Kinetics of hydrodeoxygenation of octanol over supported nickel catalysts: a mechanistic study

Palla, Venkata Chandra Sekhar; Shee, Debaprasad; Maity, Sunil K.

doi:10.1039/c4ra06826b

Cited by 27 publications

(10 citation statements)

References 30 publications

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“…First, the energies of the following reactions were calculated: Aldehydes are typical products resulting from alcohol dehydrogenation . While alkanes and alkenes are also known to result from alcohol dehydrogenation, this study specifically focuses on the dehydrogenation reaction leading to aldehydes.…”

Section: Resultsmentioning

confidence: 99%

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Alkyl-Chain-Length and Temperature Dependencies of Sensor Responses to Aliphatic Alcohols in Nanostructured Pt-Based Sensors

Hamanaka,

Tanaka,

Uchida

2023

ACS Appl. Nano Mater.

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Long-alkyl-chain alcohols are promising biofuel alternatives to fossil fuels; however, their detection has been a challenging task. In this study, the responses of nanoscale Pt-based sensors to aliphatic alcohols were examined, focusing on alkyl-chainlength and temperature dependencies. Atomistic simulations with a universal neural network potential were used to analyze the reaction and activation energies. Two types of Pt-based sensors were fabricated: a Pt nanosheet resistor sensor (PtNS) and a Pt nanoparticle-decorated graphene field-effect transistor sensor (PtNP-GFET). PtNP-GFET exhibited considerably higher sensor responses to 1-heptanol than to ethanol at 225 °C; moreover, PtNS showed the opposite alkyl-chain-length dependence compared to the response of PtNP-GFET at the same temperature. At a lower temperature of 150 °C, the sensor response toward ethanol and 1-heptanol in the case of PtNP-GFET was nearly identical, indicating that the response was primarily influenced by the concentration of hydroxyl groups. Atomistic simulation analysis revealed that the dehydrogenation reaction of the hydrocarbons near the hydroxyl groups was thermodynamically more favorable on the Pt 147 nanocluster than on the Pt(111) surface. The dehydrogenation from the alkyl chain by PtNP was confirmed in alkanes; this dehydrogenation caused a higher sensor response of PtNP-GFET to 1-heptanol than to ethanol at 225 °C. Overall, employing nanomaterials, namely nanostructured Pt catalysts and a graphene-FET transducer, and using multiple sensing temperatures are key factors for realizing long-alkyl-chain alcohol recognitions. A low temperature of 150 °C is suitable for hydroxyl group sensing, while a high temperature of 225 °C is preferable for hydrocarbon group sensing.

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Section: Resultsmentioning

confidence: 99%

“…Aldehydes are typical products resulting from alcohol dehydrogenation. 42 While alkanes and alkenes are also known to result from alcohol dehydrogenation, 43 this study specifically focuses on the dehydrogenation reaction leading to aldehydes. Figures 7a and 7b show the optimized configurations for the IS, TS, and FS.…”

Section: Origin Of the Difference In Sensormentioning

confidence: 99%

Alkyl-Chain-Length and Temperature Dependencies of Sensor Responses to Aliphatic Alcohols in Nanostructured Pt-Based Sensors

Hamanaka,

Tanaka,

Uchida

2023

ACS Appl. Nano Mater.

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“…The silica supported nickel catalyst was used as the hydrogenation catalysts. The catalyst was prepared by wetness impregnation method and the details of the preparation and characterization of silica-supported nickel catalyst and the reactor can be found elsewhere. , The elemental composition (CHNS-O), density, and viscosity of virgin and hydrogenated liquid hydrocarbon products and gasoline were measured by an elemental analyzer (Flash 2000, Thermo-Fisher Scientific), specific gravity bottle, and rheometer (MCR-302, Anton-Parr), respectively. The lower calorific value of the liquid products was measured with the help of a bomb calorimeter (Toshniwal Tech.…”

Section: Methodsmentioning

confidence: 99%

One-Step Conversion of n-Butanol to Aromatics-free Gasoline over the HZSM-5 Catalyst: Effect of Pressure, Catalyst Deactivation, and Fuel Properties as a Gasoline

Palla,

Shee,

Maity

et al. 2023

ACS Omega

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Sustainable production of gasoline-range hydrocarbon fuels from biomass is critical in evading the upgradation of combustion engine infrastructures. The present work focuses on the selective transformation of n-butanol to gasoline-range hydrocarbons free from aromatics in a single step. Conversion of n-butanol was carried out in a down-flow fixed-bed reactor with the capability to operate at high pressures using the HZSM-5 catalyst. The selective transformation of n-butanol was carried out for a wide range of temperatures (523−563 K), pressures (1−40 bar), and weight hourly space velocities (0.75−14.96 h −1 ) to obtain the optimum operating conditions for the maximum yields of gasoline range (C 5 −C 12 ) hydrocarbons. A C 5 −C 12 hydrocarbons selectivity of ∼80% was achieved, with ∼11% and 9% selectivity to C 3 −C 4 paraffin and C 3 −C 4 olefins, respectively, under optimum operating conditions of 543 K, 0.75 h −1 , and 20 bar. The hydrocarbon (C 5 −C 12 ) product mixture was free from aromatics and primarily olefinic in nature. The distribution of these C 5 −C 12 hydrocarbons depends strongly on the reaction pressure, temperature, and WHSV. These olefins were further hydrogenated to paraffins using a Ni/SiO 2 catalyst. The fuel properties and distillation characteristics of virgin and hydrogenated hydrocarbons were evaluated and compared with those of gasoline to understand their suitability as a transportation fuel in an unmodified combustion engine. The present work further delineates the catalyst stability study for a long time-on-stream (TOS) and extensive characterization of spent catalysts to understand the nature of catalyst deactivation.

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“…Since the product mixtures obtained upon catalytic conversion of pine lignocellulose in sc-MeOH using Cu20-PMO consisted of mainly aliphatic alcohols, establishing a suitable HDO procedure seemed feasible. Indeed, several catalytic systems, including the use of bifunctional catalysts 46,47 or the combination of a solid acid and hydrogenation catalyst 48,49 have been reported for HDO of aliphatic alcohols and phenolics to alkanes. In our case, the large excess of methanol and the complexity of product mixtures and possible etherication reactions are expected to be the major challenge.…”

Section: Hdo Of Aliphatic Alcohol Model Compoundsmentioning

confidence: 99%

Two-step catalytic conversion of lignocellulose to alkanes

2019

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Direct conversion of lignocellulose to alkanes is challenged by the complex and recalcitrant nature of the starting material. Generally, alkanes are obtained from one of the main lignocellulose constituents (cellulose, hemicellulose or lignin) after their separation, and platform chemicals derived therein. Here we describe a two-step methodology, which uses unprocessed lignocellulose directly, targeting a mixture of alkanes. The first step involves the near-complete conversion of lignocellulose to alcohols, using a copper doped porous metal oxide (Cu-PMO) catalyst in supercritical methanol. The second step comprises a novel solvent exchange procedure and the exhaustive hydrodeoxygenation (HDO) of the complex mixture of aliphatic alcohols, obtained upon depolymerization, to C 2 -C 10 alkanes by either HZSM-5 or Nafion at 180 C in conjunction with Pd/C in dodecane. This describes an unprecedented two-step process from lignocellulose to hydrocarbons, with an overall carbon yield of 50%.

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Kinetics of hydrodeoxygenation of octanol over supported nickel catalysts: a mechanistic study

Cited by 27 publications

References 30 publications

Alkyl-Chain-Length and Temperature Dependencies of Sensor Responses to Aliphatic Alcohols in Nanostructured Pt-Based Sensors

Alkyl-Chain-Length and Temperature Dependencies of Sensor Responses to Aliphatic Alcohols in Nanostructured Pt-Based Sensors

One-Step Conversion of n-Butanol to Aromatics-free Gasoline over the HZSM-5 Catalyst: Effect of Pressure, Catalyst Deactivation, and Fuel Properties as a Gasoline

Two-step catalytic conversion of lignocellulose to alkanes

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